Production of polyallyl-type alcohols from polyallyl-type formates



Patented Mar. 13, 1951 PRODUCTION OF POLYALLYL'rTYPE ALCO- HOLS FROM POLYALLYL-TYPE FOR/MATES Richard R. Whetstone, Berkeley, and Theodore W. Evans, Oakland, Calif., assignors to Shell Development'Company, San Francisco, Calif., a corporation of Delaware No Drawing. Application March 17, 1947,

Serial'No. 735,256

This invention relates to a process for theproduction of polyallyl-type alcohols. More particularly the invention relates to a process for the manufacture of polyallyl-type alcohols from a polymer of a formic acid ester of an allyl-type alcohol.

V More specifically, the invention provides a practicaland highly economical method for the production of relatively pure polyallyl-type alcohols from esters oi'formic' acid and allyl-type 10 Claims. (Cl. 260-913) alcohols which comprises reacting a polymer of the formic acid ester of the allyl-type alcohol with water and a monohydrio alcohol in the presence of formic acid, and removing, preferably by distillation, the formic acid ester of the monohydric alcohol substantially as fast as it is formed in the reaction. The polyallyl-type alcohols produced by the process of the invention have a relatively low production cost and possess a very high degree of purity and chemical activity. Such properties are far superior to those of the polyallyl-type alcohols produced by the previously known methods of production and enable the polyallyl-type alcohols produced by the invention to be used for many important industrial applications for which the inferior products of the prior art are entirely unsuited.

Polyallyl-type alcohols, i. e. polymers of monomeric allyl-type alcohols, have shown promise as replacements for glycerol in the production of alkyl resins and in the production of synthetic and semi-synthetic drying oils. The polyallyltype alcohols are particularly adaptive to this type of utility as they possess a plurality of free hydroxyl groups which are presumably all primary and therefore readily undergo esterification. The structure of the polyallyl-type alcohols is not definitely known but is presumed that they have a general structure which is conveniently represented by a probable structural formula for polyallyl alcohol: r

which is dependent upon the number of monomer units present in the polymer. The above possible structure is suggested only for a better understandin of the invention, andit should be understood that the-invention is not to be construed as limitedtopolymers of such a structure.

Various methodsare'known for the production of the above-described polyallyl-type alcohols but they have met with suchdifiiculties as to discourage their use to produce the polyallyl type-I alcohols on a commercial scale. A direct polymerization of the allyl-type alcohols in general proceeds'slowly and incompletely and requires the presence of oxygen-yielding polymerization catalysts for best results. This method-does not yield a suitable product as the oxygen-yielding catalyst oxidizes the free primary hydroxyl groups to some extent to aldehyde and/or car.-' boxyl' groups and the presence of such groups causes a discoloration of the polyallyl-type a1- cohols. The method of producin the polyallyltype alcohols by the water hydrolysis of some of the esters of the polyallyl-type alcohols, such as allyl formate, has proven unfeasible as the product is produced in low yields and is difficult to l purify to the extent desired for commercial pur- The use of methods depending upon an alkaline hydrolysis of the esters of the polyallyltype alcohols has, likewise, proved unfeasible as it requires large amounts of alkali, i. e. one equiv- DOSES;

' type alcohols by treating the esters with low boiling alcohols have the disadvantage of requiring relatively-expensive alcoholates as'catalysts and requiring'lon reaction periods and cumbersome methods for the separation of the final product from the reaction mixture. In general, the

known methods are either too expensive or give too impure products to enable the polyallyl-type alcohols to be produced on a scale Where they might successfully compete with glycerol and pentaerythritol in the applications described above; 7 W I It is an'object of the invention, therefore, to

provide a practical method for the production of polyallyl type alcohols which avoids the difliculties of the previously known method and enables the production of the polymeric alcohols in an efficient andeconomical manner. It is a further object of the invention to provide a method of manufacture of polyallyl-type alcohols which avoids the use of expensive catalysts and 5 employs avery simple and convenient method for the separation of the final product from reaction mixture. It is a further object of the infvention to provide a process'for the production qi ectlr to a satur ea e rpir afiom w ch "in 3 4 r of polyallyl-type alcohols which produces high termed the alpha carbon atom and the iirisat yields of polymeric alcohols which are relatively urated carbon atoms are the beta, gamma carpure, possess a high resistance to discoloration bon atoms. and possess a plurality of active primary hy- Preferred organic radicals which Rmay repdroxyl groups. Other objects fof.v the inyention 5 resent in the abovedeseribed foritrfifilafor the will be apparent from the detailed description ally'l-type alcohols are the hydrocarbon radicals.

given hereinafter. Such hydrocarbon. radicals are monovalent and It has now been discovered that polyallyl-typ' may be substituted or unsubstituted, saturated alcohols may be produced in japractical; a ece: or unsaturated, cyclic or alicyclic or aromatic. nomical manner by the novel method of reacting i0 Examplesof the hydrocarbon radicals which R a polymer of a formic acid,ester of an allylmay represent are methyl, ethyl, propyl, n-butyl, type alcohol with Water and a nionliydric al "tylyn'fl-pentyl, 2-' chloroethyl, hexyl, 2,4-dicohol in the presence of formic acidand remgvg chlor y lo xvl -tri thy1d t yl ing preferably by distillation, the formic acid vinyl arbi'riyl phenyl, tolyl, 2-chlorophenyl, 3- ester of the monohydric alcohol from the reac l5 aceto-cyclohexyl, anthr-yl, 3ebromo-2-cyclohextion mixture substantially as fast asit is fo 'd e'r yl; 3-"vii1yl 2- cyclohexenyl, z-chlorocyclopentyl,

therein. It has further been discovered that the and fi-nitro-butyl. The more preferred hydropolyallyl-type alcohols produced by theprocess carbon radicals which R may represent are the of the invention are formed in relatively high alkyl radicals, preferably the lower alkyl radicals, eld iandvpqs es elh shi egree f Prui t 5 20 sme h hyli q le butyl up to those e stance- 9 $1 .91 H9 1 elleef r e fiifi '8 "Din a m v r r other polyhydi ic alcohols in those utilities dernandinga relatively pure and reactive pe itn l ol, 3(3-bromo 2 '-"eycloliekenyl= 2- olyhy r cr mp ndr r t fIhe exact natureof the reaction 'occnrri rap rticularly br'r'er'r the execution of the process of thei'nv alcohols are those bet items .36 e 'a i examples bf t qie ref rre lylr ii 'el 'e le a whe ferredtonseihe .al l-t neee sph lf m r in L l me a lfi plp, l1y1a1Q0h91/ T mater ecoye ed ro t e.siie lleilntmeybe r?- cycle and u ed in. the.p 9d1, =ti9 ,9 'ymer ic 'ally -t p rfo maie ier i l m i 1i thisw r a eefi res i qeiheu oetei P're i th,e;po1yallyl-typealcoholsin the desired purified The pbiral yl-i peEmirateu ed j p thei e iio i thej lrmerpf a atta ed Itilrnis ttached arr'eoy to rte hyd 'xyl I p.

ilih far s at ms, l hl is he- 5 carbon atoms in an open chain, for exampl he formic acid and the allyl-type alooli'oltoiirddfie v arbon atoms in N iphatic radicals an d also the the polymericfdrmatefivhlichfis a f adtant in the 'parbonato nsin cyGLQQIibha Ci d CaIS e g he 'process of the invention, may be accomplished .oh ato si t e qyq qhexy ,n cy 'yl by any suitable polymerization method. Such radicals. Allyl-type alcohols have the structure 5 {mqthqds rinpludes'tfie polymizi z fionpf t wher in. maeir rr jerejt a nees a. n logenua omro l n Dreams. qi eL,

inic cidesjtersjythe" pplication offheatjli-gh t,

'entco the rou om ie .,i h rp i some, o l ti er. else, be .1 's r h carbon atom bearin the hydroxyl gro w re to the particular molecular weight desired.

Temperature of from about 70 C. to about 90 C. produce polymers having a molecular weight of around 2000. As the temperature is increased the molecular weight of the polymer decreases until at about 250 C. the molecularv weight is about 500. Polymers of the esters of formic'acid and the allyl-type alcohols having molecular weights in the rangev of about 2000 to about 500 have given very'satisfactory results in the process of the invention. and the polymerization temperatures of about 70 C. to about 250 C. are therefore the more preferred. High or lower temperatures, however, may be used if deemed desirable or necessary. The preferred polymerization reaction is conducted in the liquid phase. The pressure to be used in each case will, therefore, depend upon the particular allyl-type formate and particular polymerization temperature to be employed. In those cases where the polymerization is to take place below the boiling point of the desired allyl-type formate atmospheric pressure is preferred, while in those instances where'the' polymerization is to take place above the boiling point of the superatmospheric pressure is required. j I

The time of polymerization will vary over a considerable perioddepending upon the particular polymerization temperature selected. 7 The time of polymerization may vary, 'for' example, from about minutes or less when a polymerization temperature of about 250 C. is used to as much as hours when a polymerization temperature of C. is employed.

' Catalysts are usually added in the polymerization process to hasten the polymerization. The preferred catalysts are those which are soluble in the polymerizable ester. Benzoyl peroxide has been found very satisfactory. *3 Other suitable polymerization catalysts are acetyl peroxide, benzoyl acetyl peroxide, lauryl peroxide, dibutyry-l peroxide, succinyl peroxide, sodium peroxide, barium peroxide,-tertiary alkyl hydroperoxide, die tertiary alkyl peroxides, peracetic acid, perphtha'lic acid, etc. The amount of the catalyst used will vary under various conditions but ordinarily will be between about 0.01% to about 5% by weight of the ester being polymerized. r

A process for the polymerization of allyl type esters in the presence of oxygen and oxygenyielding catalyst is described more completely in the copendin application of Adelson and Dannenberg Serial No. 417,278; filed October 31, 1941 now abandoned.

The esters may be polymerized in bulk in the presence or absence of a solvent or diluent. The use of solvents such as iso-octane' in some cases tend to assist in decreasing'the molecular weight of the final polymer. The polymerizationmay be carried to completion without substantial interruption or it may be stopped at any-point short of completion to' obtain the desired extent "of polymerization. p

The polymers of formic acid and the allyl- -type "alcohols producedby any suitable method "are ester d treated, according to the process of the inve i tion, with water and a monohydric alcohol in the presence of formic acid to convert the polymer into a polyallyl type alcohol. The allyl type alcohol identical to the one used in producing the polymeric formic acid ester is the more preferred of the monohydric alcohols to be used in the reaction. However, other monohydric alcohols may be used. It is preferred, in general, that the other alcohols used be the lower members of the series which contain not more than 6 carbon atoms in the molecule, while the monohydric alcohols containing not more than 4 carbon atoms are still more preferred. The monohydric alcohols may be either saturated or unsaturated. Representative examples of suitable monohydric alcohols are methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, the amyl alcohols, the hexyl alcohols, cyclohexanol, allyl-alcohol, beta-metliallyl alcohol, methyl vinyl carbinol, cyclopentanol, propargyl alcohol and the like. The primary alcohols are the more preferred as it is found that they have greater reactivity than the secondary alcohols.

.present in the polyallyl-type formate molecule.

Larger amounts may be used, but in general, add nothing to the efficiency of the process. Particularly fine results in yield and purity of product are obtained when the amount of the monohydric .alcohol taking part in the reaction varies between about 2 to about 4 moles for every formate group present in the polyallyl-type formate molecule, and such a range is the more preferred for the process.

'- The amount of water added to the reaction mixture to effectuate the combined hydrolysisalcoholysis reaction may vary over a considerable range. The amounts of water added may, for example, vary from as high as 48 moles per formate group present in the polyallyl-type formate molecul'e to as low as about 2 moles per formate group.

. Small amounts of water, i. e. about 2 to about 6 moles per formate group, in general, produce the desired results, are much more efficient to handle and are, therefore, the more preferred amounts of water to be used in the reaction.

The quantity of formic acid catalyst to be add ed to the reaction mixture may vary over a wide range depending upon the particular polyallylacid as small as 2% to about 4% by weight of the polyallyl-type formate being treated usually give eificient reaction rates and are I the preferred quantities of catalyst to be employed.

- The combined hydrolysis-alcoholysis reaction takes place at low temperaturesi. e. around room temperatures, butit has been found advantatraces. of impurities. The residue remainingin the flask is relatively pure, solid polyallyl alcohol.

Example'IV V Polym'ethallyl formate is produced by subjecting liquid methallylformate containing about 2% by weight of di-tertiary butyl peroxide to atemperature of about 210 C. The resulting polymer mate water azeotrope is distilled off by alternate total reflux and total take ofl. After about hours of treatment approximately 90% of the methallyl formate has been recovered. A further distillation of the mixture removes the last traces asagg sz atoms withwater and a monomeric betagammamonoolefinic monohydricjalCohol id entical with the one used in the preparation of the said polymer, in the 'presenceof ;01% 170.5% bywe hto formic acid based on the weightof the polymer of formic acid ester, removing the formed ester of formic acid and the monomeric monohydric alcoe hol from the reaction mixture substantially as fast as it is formedv therein, the monomeric beta,gamm-a-monoolefinic monohydric alcohol and water. being added to the initial reaction of water and methallyl alcohol and leaves as-residue in the flask solid polymethallyl alcohol.

Example V Approximately 201 parts of the polymethallyl formate produced in Example IV is heated under adistillation column with about 550 parts of butyl 7 alcohol and about 215 parts of water with about 5 parts of formic acid. The butyl formate water azeotrope is distilled over to give a 90% recovery in about 10 hours of treatment. Continued distillation removes Water and butyl alcohol and gives as residue in the flask, .very light yellow, solid polymethallyl alcohol.

We claim as our invention:

1. A process for the production of polyallyl alcohol which comprises reacting polyallyl formate with water and a monohyclric alcohol of the group consisting of beta-gamma monoolefinic, monohydric, alcohols containing from 3 to 18 carbon atoms and saturated, monohydric alcohols containing from 1 to 6 carbon atoms, in the presence of 2% to 4% by Weight of formic acid based on the weight of the polyallyl formate, and removing the formed ester of the monohydric alcohol and formic acid from the reaction mixture substantially as fast as it is formed therein, the monohydric alcohol and water being added to the initial reaction mixture in such quantities that there will be at least in excess of one mole of monohydric alcohol and at least two moles of water for each formate group present in the polyallyl formate molecule.

2. A process for producing polyallyl alcohol which comprises heating polyallyl formate with allyl alcohol and water in the presence of .01% to 5% by weight of formic acid based on the weight of the polyallyl formate, removing the formed allyl formate from the reaction mixture substantially as fast as it is formed therein, the allyl alcohol and water being added to theinitial reaction mixture in such quantities that there is at least in excess of one mole of allyl alcohol,

and at least two moles of water for every form-ate group present in the polyallyl formate molecule,

" and said heating being conducted at a temperature between 50 C. and the decomposition temperature of the polymers present in the reaction Iriixture.

' 3. A process for producing a polymer of a beta,gamma-monoo1eflnic, monohydric alcohol containing from 8 to 18 carbon atoms which comprises reacting a polymer of an ester of (1) formic acid and (2) a betagamma-monoolefinic, monomixture in such quantities that there will beat least in excess of one mole of the said monomeric monohydric alcohol and at least two moles. of water for every. formate-group present in' the polymer of the formic acid ester. I 4. A process for preparing polyallyl alcohol which. comprises heating, polyallyl formate with allyl alcohol 'and waterin the presence.o'f,3% by weight of formic-acidb'ased'on the weightof the polyallyl formate, at "a temperature'b'etween 501 C. and 150 C., and removing-allyl formatefromp the reaction mixtureby distillationsubstantially as fast as it is formed therein-the allyl alcohol and water being added to the initial reaction mixe ture in such quantities that there are 4 moles of alcohol and -5 moles-ofwater for every formate group present in the polyallyl formate molecule.

5. A process "for preparing polyallyl alcohol which comprises heating polyallyl formate with ethyl alcohol'aiid water in the presence of 2% by weight of formic aicd based on the weight of the polyallyl formate, at a. temperature between C and the decomposition temperature of the polymers present. in the..,mixtu're, and removing ethyl formate from the reaction mixture by distillation substantially as fast as it is formed therein, the ethyl alcohol and water being added to the initial raction mixture in such quantities that there is between 2 and 4 moles of alcohol and between 2 and 6 moles of water for every formate group present in the polyallyl formate molecule.

6. A process for preparing polymethallyl alcohol which comprises heating polymethallyl formate with methallyl alcohol and water in the .2 and 4 moles of methallyl alcohol and 2 to 6 moles of water for every formate group present 7 in the polyallyl formate molecule.

'7. A process for producing polyallyl alcohol which comprises heating polyallyl formate with allyl alcohol and water in the presence of 2% to 4% by weight of formic acid based on the of polyallyl formate, at a temperature between 50 C. and 150 C., and removing allyl' formate from the reaction mixture substantially as fast as it is formed therein, the allyl alcohol and water being added to the initial reaction mixture in such quantities that there is between 2 and 4 moles of allyl alcohol and 2 to 6 moles of water for every formate group present in the polyallyl formate molecule.

8. A process for producing a polymer of a beta,

gamma-monoolefinic monohydric alcohol which comprises heating a polymer of an ester of (1) formic acid and (2) a beta,gamma-monoolefinc monohydric alcohol containing from 3 to 18 carhydric alcohol containing from 3 to 18 carbon bon atoms with water and a monomeric beta,

weight 6 moles oiwater for every form-ate ester group nreeent in a in'oiecul'e of the said olymer of the formic acid ester.

9. A process fonpr'oducin a'poiymerof a beta, gamma-monoolefini'c 'monoh ydfic "alcohol which comprises heatinga polymer of an ester of formic acid anti a betagamma-monoolefinic monohydric alcohol containing. from 3' to "18 carbon atoms' with water and a' saturated alipinitio monohydric alcohoi containing" from 1 to 6 carbon'at'oms in the'presence of 111% to 5% by weightof formic acid hasedon the weight of the "eaid' polymer of formic acid ester, vat a tern- 'pei'ature between 50 Cfand 150 CL, and remow ifig the onom ric 631781 Of formic acid and the saturated mononydric alo-ohoi by distillation a's faet as it is formed therein, the beta, gammaiifofioole'fiiiic fii'onohydfic' alcohol and water being added to" the initial reaction mixtufe in such quantities that th'e'ie is between-'2 and '4moles or 'alconoi and" 2' to 6 moles of water for every oi z'n'ate *groii'p present in the said polymer of the 1o. Alprocesrs for producing a-polymer of a 35 2,467,105

on atoms the presence- V 12 beta-gammaamonoolefinic -monohydric. alcohol Whichnomprises reacting a poiymerof'an ester of 'gl) formic acid and-(2:) a beta,gamma-monoolefimc monohydric. alcohol containingnfromi 3 to 'lfl'cazcbonat'oms with Water and a ,monohydric alcohol of the groupconsisting of beta,gammamonoolefinic m'onohydr-i'c V alcohols containing from 3:130 18 carboniatoms and saturated mono hydr'i'c' alcohols containing from 11 to 6 carbon atoms in the presence of .0l% to 5% by Weight of formic acid" based on the weight of the ,polymerof the. formic "acid .ester,. and

removing the monomeric ester .of formic acid and the monoh-yciric. alcoholifrom the reaction substantially as fastas it is formedtherein, the monohyd-ric alcohol andwater being added tothe initial reaction mixture in vsuch quantities that there Will be at least in excess'of 1 mole of alcohol and at l eastfl molesv of water for evefy fermate group present in the polymer offthe formic acid ester. RICHARD R. WHETSTONE. THEODORE W. EVANS.

REFERENES CITED The following references are of. record in the file of this patent:

' UNITED STATES PATENT-S 30 Number Name Date 2,430,372 Stamatoif Nov; l, 1947 2,332,900 DAlelio Oct. 26, 1943 2,360,308 Thomas et al YOct. 10, 1944 2,378,169 Agre et a1; June 12,1945 Adelson-e't al Apr. 12, 1949 

10. A PROCESS FOR PRODUCING A POLYMER OF A BETA GAMMA - MONOOLEFINIC MONOHYDRIC ALCOHOL WHICH COMPRISES REACTING A POLYMER OF AN ESTER OF (1) FORMIC ACID AND (2) A BETA,GAMMA-MONOOLEFINIC MONOHYDRIC ALCOHOL CONTAINING FROM 3 TO 18 CARBON ATOMS WITH WATER AND A MONOHYDRIC ALCOHOL OF THE GROUP CONSISTING OF BETA,GA,,AMONOOLEFINIC MONOHYDRIC ALCOHOLS CONTAINING FROM 3 TO 18 CARBON ATOMS AND SATURATED MONOHYDRIC ALCOHOLS CONTAINING FROM 1 TO 6 CARBON ATOMS IN THE PRESENCE OF .01% TO 5% BY WEIGHT OF FORMIC ACID BASED ON THE WEIGHT OF THE POLYMER OF THE FORMIC ACID ESTER, AND REMOVING THE MONOMERIC ESTER OF FORMIC ACIF AND THE MONOHYDRIC ALCOHOL FROM THE REACTION SUBSTANTIALLY AS FAST AS IT IS FORMED THEREIN, THE MONOHYDRIC ALCOHOL AND WATER BEING ADDED TO THE INITIAL REACTION MIXTURE IN SUCH QUANTITIES THAT THERE WILL BE AT LEAST IN EXCESS OF 1 MOLE OF ALCOHOL AND AT LEAST 2 MOLES OF WATER FOR EVERY FORMATE GROUP PRESENT IN POLYMER OF THE FORMIC ACID ESTER. 